WO2024106910A1 - Électrolyte pour batterie secondaire au lithium et batterie secondaire au lithium le comprenant - Google Patents

Électrolyte pour batterie secondaire au lithium et batterie secondaire au lithium le comprenant Download PDF

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WO2024106910A1
WO2024106910A1 PCT/KR2023/018273 KR2023018273W WO2024106910A1 WO 2024106910 A1 WO2024106910 A1 WO 2024106910A1 KR 2023018273 W KR2023018273 W KR 2023018273W WO 2024106910 A1 WO2024106910 A1 WO 2024106910A1
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group
electrolyte
formula
compound
carbonate
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PCT/KR2023/018273
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English (en)
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Ha Na Ra
Tae Jin Lee
Min Seo Kim
Myung Heui Woo
Hye Jin Park
Bo Kyung Ryu
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Samsung Sdi Co., Ltd.
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Publication of WO2024106910A1 publication Critical patent/WO2024106910A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • One or more embodiments of the present disclosure relate to an electrolyte for a lithium secondary battery and a lithium secondary battery including the electrolyte.
  • Lithium secondary batteries have three or more times higher energy density per unit weight than existing lead-acid batteries, nickel-cadmium batteries, nickel-metal hydride batteries, and/or nickel-zinc batteries and are capable of being charged at a high speed.
  • Lithium secondary batteries should be stable within a battery operating voltage range and should maintain safety even beyond the operating voltage range. However, in some lithium secondary batteries, lithium excessively flows out of a positive electrode and excessively flows into a negative electrode under an overcharge and overvoltage environment. Thus, both (e.g., simultaneously) the positive and the negative electrode are in an unstable state under the overcharge and overvoltage environment.
  • one or more additives are added to an electrolyte, resulting in some degradation in performance of a lithium secondary battery.
  • One or more aspects of embodiments of the present disclosure are directed toward an electrolyte for a lithium secondary battery which includes a electrolyte additive.
  • One or more aspect of embodiments of the present disclosure are directed toward a lithium secondary battery including the electrolyte.
  • an electrolyte for a lithium secondary battery includes a lithium salt
  • At least one selected from among R 1 to R 6 may be a
  • C1-C5 alkyl group including a cyano (CN) group one or two selected from among R 1 to R 6 may each be a fluorinated C1-C5 alkyl group, and the remainder of R 1 to R 6 are independently hydrogen, a substituted or unsubstituted C1-C5 alkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C2-C10 alkynyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C7-C50 alkylaryl group, or a substituted or unsubstituted C6-C50 heteroaryl group.
  • CN cyano
  • a lithium secondary battery includes a positive electrode which includes a positive electrode active material
  • a negative electrode which includes a negative electrode active material
  • the electrolyte for a lithium secondary battery may form a film on a positive electrode under an overcharge and overvoltage environment to protect the positive electrode and suppress or reduce a voltage rise of a battery, thereby suppressing electrolyte decomposition. Therefore, when such an electrolyte is adopted, a positive electrode may be protected in an overcharge environment, thereby providing a lithium secondary battery having improved safety and also having improved life characteristics at a high temperature.
  • FIG. 1 is a schematic view of a lithium secondary battery according to one or more embodiments of the present disclosure.
  • FIG. 2 shows results of a linear sweep voltammetry test on three-electrode beaker cells utilizing electrolytes according to Examples 1 and 2 and Comparative Example 1 according to one or more embodiments of the present disclosure.
  • the term “and/or” includes any and all combinations of one or more of the associated listed items. As utilized herein, the term “or” refers to the term “and/or” As utilized herein, the expression “at least one species,” “at least one” or “one or more” in front of elements refers to that the expression may complement the entire list of elements and does not refer to that the expression may complement individual elements described above.
  • an overcharge property improving additive has a structure including a biphenyl group.
  • electrolyte decomposition may start, which may increase internal resistance of a cell and degrade performance such as life characteristics of the battery.
  • an electrolyte for a lithium secondary battery may include a lithium salt, an organic solvent, and an additive represented by Formula 1.
  • At least one selected from among R 1 to R 6 may be a C1-C5 alkyl group including a cyano (CN) group,
  • R 1 to R 6 may each be a fluorinated C1-C5 alkyl group
  • R 1 to R 6 may each independently be hydrogen, a substituted or unsubstituted C1-C5 alkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C2-C10 alkynyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C6-C50 alkylaryl group, or a substituted or unsubstituted C6-C50 heteroaryl group.
  • one or two selected from among R 1 to R 6 may each be a C1-C5 alkyl group including a CN group.
  • Non-limiting examples of the C1-C5 alkyl group including the CN group may include -CH 2 CN, -CH 2 CH 2 CN, -CH 2 CH 2 CH 2 CN, and/or the like.
  • Non-limiting examples of the fluorinated C1-C5 alkyl groups may include CF 3 and C 2 F 5 .
  • the additive represented by Formula 1 may include the C1-C5 alkyl group including the CN group to protect a surface of a positive electrode, thereby contributing to structural stabilization of the positive electrode. Because the additive represented by Formula 1 has a structure in which a phenyl group is substituted with the fluorinated C1-C5 alkyl group, the additive may have excellent or suitable flame retardancy and may be preferentially oxidized, thereby serving to suppress or reduce a voltage rise of a battery in a high voltage environment.
  • the electrolyte for a lithium secondary battery includes the additive represented by Formula 1
  • a film may be formed on a positive electrode to protect the positive electrode under an overcharge and overvoltage environment, and the electrolyte may start to be decomposed at a voltage of about 4.5 V or more, thereby suppressing a voltage rise of a battery in an overcharge environment to prevent or reduce electrolyte decomposition. Accordingly, in a lithium secondary battery including the electrolyte, it may improve overcharge characteristics and improve safety, and maintain performances such as high-temperature life characteristics or minimize or reduce degradation in the performances.
  • the additive may be at least one selected from compounds represented by Formulas 1-1 to 1-4.
  • R 3 to R 6 may each independently be hydrogen, a C1-C5 alkyl group, a C2-C10 alkenyl group, a C2-C10 alkynyl group, a C3-C20 cycloalkyl group, a C6-C50 aryl group, a C7-C50 alkylaryl group, or a C6-C50 heteroaryl group, and n may be an integer from 1 to 4.
  • R 2 and R 4 to R 6 may each independently be hydrogen, a C1-C5 alkyl group, a C2-C10 alkenyl group, a C2-C10 alkynyl group, a C3-C20 cycloalkyl group, a C6-C50 aryl group, a C7-C50 alkylaryl group, or a C6-C50 heteroaryl group, and n may be an integer from 1 to 4.
  • R 2 , R 3 , R 5 , and R 6 may each independently be hydrogen, a C1-C5 alkyl group, a C2-C10 alkenyl group, a C2-C10 alkynyl group, a C3-C20 cycloalkyl group, a C6-C50 aryl group, a C7 -C50 alkylaryl group, or a C6-C50 heteroaryl group, and n may be an integer from 1 to 4.
  • R 3 , R 4 , and R 5 may each independently be hydrogen, a C1-C5 alkyl group, a C2-C10 alkenyl group, a C2-C10 alkynyl group, a C3-C20 cycloalkyl group, a C6-C50 aryl group, a C7-C50 alkylaryl group, or a C6-C50 heteroaryl group, and n and m may each independently be an integer of 1 to 4.
  • R 3 to R 6 may all be, for example, hydrogen.
  • R 2 and R 4 to R 6 may all be, for example, hydrogen.
  • R 2 , R 3 , R 5 , and R 6 may all be hydrogen, and in Formula 1-4, in some embodiments, R 3 , R 4 , and R 5 may all be hydrogen.
  • the additive represented by Formula 1 may be, for example, at least one selected from Compounds A to I.
  • a content (e.g., amount) of the additive represented by Formula 1 may be in a range of about 0.1 wt% to about 10 wt%, about 0.3 wt% to about 10 wt%, about 0.5 wt% to about 10 wt%, about 1 wt% to about 10 wt%, about 1 wt% to about 7 wt%, about 1 wt% to about 7 wt%, about 1 wt% to about 5 wt%, or about 1 wt% to about 4 wt%, with respect to about 100 wt% of the total weight of the electrolyte.
  • the content (e.g., amount) of the additive is within the above range, a positive electrode may be protected in a high temperature environment to increase a lifetime of the positive electrode and improve overcharge characteristics.
  • the lithium salt may include at least one selected from LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiClO 4 , LiCF 3 SO 3 , Li(CF 3 SO 2 ) 2 N, LiC 4 F 9 SO 3 , LiAlO 2 , LiAlCl 4 , LiN(C x F 2x+1 SO 2 )(C y F 2y+1 SO 2 ) (wherein 2 ⁇ x ⁇ 20 and 2 ⁇ y ⁇ 20), LiCl, LiI, lithium bis(oxalato)borate (LiBOB), and compounds represented by Formulas 2 to 5, but embodiments of the present disclosure are not limited thereto. Any material usable as a lithium salt in the art may be utilized.
  • a concentration of the lithium salt in the electrolyte may be in a range of about 0.1 M to about 5.0 M, for example, a range of about 0.1 M to about 3.0 M, or about 0.1 to about 2.0 M. When the concentration of the lithium salt is within the above range, it may obtain further improved characteristics of a lithium secondary battery.
  • the organic solvent may be at least one selected from a carbonate-based solvent, an ester-based solvent, an ether-based solvent, and a ketone-based solvent.
  • the carbonate-based solvent may include ethyl methyl carbonate (EMC), methyl propyl carbonate (MPC), ethyl propyl carbonate (EPC), dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC), and/or the like.
  • EMC ethyl methyl carbonate
  • MPC methyl propyl carbonate
  • EPC ethyl propyl carbonate
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • DPC dipropyl carbonate
  • PC propylene carbonate
  • EC ethylene carbonate
  • BC butylene carbonate
  • the ester-based solvent may include methyl propionate, ethyl propionate, ethyl butyrate, methyl acetate, ethyl acetate, n-propyl acetate, dimethyl acetate, gamma butyrolactone, decanolide, gamma valerolactone, mevalonolactone, caprolactone, and/or the like.
  • the ether-based solvent may include dibutyl ether, tetraglyme, diglyme, dimethoxyethane, 2-methyl tetrahydrofuran, tetrahydrofuran, and/or the like.
  • the ketone-based solvent may include cyclohexanone and/or the like.
  • the nitrile-based solvent may include acetonitrile (AN), succinonitrile (SN), adiponitrile, and/or the like.
  • Other suitable solvents may include dimethylsulfoxide, dimethylformamide, dimethylacetamide, tetrahydrofuran, and/or the like, but embodiments of the present disclosure are not necessarily limited thereto.
  • Any material utilized as an organic solvent in the art may be utilized.
  • the organic solvent may include a mixed solvent of about 50 vol% to about 95 vol% of chain carbonate and about 5 vol% to about 50 vol% of cyclic carbonate, for example, a mixed solvent of about 70 vol% to about 95 vol% of chain carbonate and about 5 wt% to about 30 vol% of cyclic carbonate.
  • the organic solvent may be a mixed solvent of three or more organic solvents.
  • the organic solvent may include at least one selected from EMC, MPC, EPC, DMC, DEC, DPC, PC, EC, fluoroethylene carbonate (FEC), vinylene carbonate (VC), vinylethylene carbonate (VEC), butylene carbonate, ethyl propionate, ethyl butyrate, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, gamma-valerolactone, gamma-butyrolactone, and tetrahydrofuran, but embodiments of the present disclosure are not limited thereto. Any material utilized as an organic solvent in the art may be utilized.
  • the electrolyte may be in a liquid or gel state.
  • the electrolyte may be prepared by adding the lithium salt and the above-described additive to the organic solvent.
  • a lithium secondary battery may include a positive electrode including a positive electrode active material, a negative electrode including a negative electrode active material, and the above-described electrolyte between the positive electrode and the negative electrode.
  • a lithium (secondary) battery may include a positive electrode including a positive electrode active material, a negative electrode including a negative electrode active material, and the above-described electrolyte between the positive electrode and the negative electrode.
  • the lithium secondary battery includes the additive of the above-described electrolyte for a lithium secondary battery, an increase in initial resistance of the lithium secondary battery may be suppressed or reduced, generation of gas due to a side reaction may be suppressed or reduced, and life characteristics of the battery may be improved.
  • the positive electrode active material may include a lithium transition metal oxide including nickel and other transition metal(s).
  • a content (e.g., amount) of nickel in the lithium transition metal oxide including nickel and other transition metal(s) may be about 60 mol% or more, for example, about 75 mol% or more, about 80 mol% or more, about 85 mol% or more, or about 90 mol% or more, with respect to the total number of moles of the transition metals in the lithium transition metal oxide.
  • the lithium transition metal oxide may be a compound represented by Formula 7:
  • M may be at least one selected from manganese (Mn), vanadium (V), magnesium (Mg), gallium (Ga), silicon (Si), tungsten (W), molybdenum (Mo), iron (Fe), chromium (Cr), copper (Cu), zinc (Zn), titanium (Ti), aluminum (Al), and boron (B), and A may be F, S, Cl, Br, or a combination thereof.
  • the lithium transition metal oxide may be at least one selected from compounds represented by Formulas 8 and 9.
  • 0.6 ⁇ x ⁇ 0.95, 0 ⁇ y ⁇ 0.2, and 0 ⁇ z ⁇ 0.1 For example, 0.7 ⁇ x ⁇ 0.95, 0 ⁇ y ⁇ 0.3, and 0 ⁇ z ⁇ 0.3.
  • the lithium transition metal oxide may be LiNi 0.6 Co 0.2 Mn 0.2 O 2 , LiNi 0.88 Co 0.08 Mn 0.04 O 2 , LiNi 0.8 Co 0.15 Mn 0.05 O 2 , LiNi 0.8 Co 0.1 Mn 0.1 O 2 , LiNi 0.88 Co 0.1 Mn 0.02 O 2 , LiNi 0.8 Co 0.15 Al 0.05 O 2 , LiNi 0.8 Co 0.1 Mn 0.2 O 2 , or LiNi 0.88 Co 0.1 Al 0.02 O 2 .
  • the positive electrode active material may include at least one active material selected from Li-Ni-Co-Al (NCA), Li-Ni-Co-Mn (NCM), lithium cobalt oxide (LiCoO 2 ), lithium manganese oxide (LiMnO 2 ), lithium nickel oxide (LiNiO 2 ), and lithium iron phosphate (LiFePO 4 ).
  • NCA Li-Ni-Co-Al
  • NCM Li-Ni-Co-Mn
  • LiCoO 2 lithium cobalt oxide
  • LiMnO 2 lithium manganese oxide
  • LiNiO 2 lithium nickel oxide
  • LiFePO 4 lithium iron phosphate
  • the negative electrode active material may include at least one selected from a silicon-based compound, a carbon-based material, a composite of a silicon-based compound and a carbon-based compound, and silicon oxide (SiO x ) (wherein 0 ⁇ x ⁇ 2).
  • the silicon-based compound may include silicon particles, silicon alloy particles, and/or the like.
  • a size of the silicon-based compound may be less than about 200 nm, for example, in a range of about 10 nm to about 150 nm.
  • size may refer to an average particle diameter when the silicon-based compound is spherical and may refer to an average long axis length when the silicon-based compound is non-spherical.
  • the size of the silicon-based compound is within the above range, life characteristics of the silicon-based compound are excellent or suitable, and thus, when the electrolyte according to one or more embodiments is utilized, a lifetime of the lithium secondary battery may be further increased.
  • the carbon-based material may be crystalline carbon, amorphous carbon, or a mixture thereof.
  • the crystalline carbon may be graphite such as natural graphite or artificial graphite having a non-shaped (e.g., irregularly shaped), plate-like, flake-like, spherical, or fibrous form.
  • the amorphous carbon may be soft carbon (low-temperature fired carbon), hard carbon, mesophase pitch carbide, and/or fired coke.
  • the composite of the silicon-based compound and the carbon-based compound may be a composite having a structure in which silicon particles are arranged on a carbon-based compound, a composite having a structure in which silicon particles are included on a surface of a carbon-based compound and inside the carbon-based compound, or a composite in which silicon particles are coated with a carbon-based compound and included inside the carbon-based compound.
  • the carbon-based compound may be graphite, graphene, graphene oxide, or a combination thereof.
  • the composite of the silicon-based compound and the carbon-based compound may be an active material obtained by dispersing silicon nanoparticles having an average particle diameter of about 200 nm or less on carbon compound particles and then coating the silicon nanoparticles with carbon or an active material in which silicon (Si) particles are present on graphite and inside graphite.
  • the composite of the silicon-based compound and the carbon-based compound may have an average secondary particle diameter of about 5 um to about 20 um.
  • An average particle diameter of the silicon nanoparticles may be about 5 nm or more, for example, about 10 nm or more, for example, about 20 nm or more, for example, about 50 nm or more, or for example, about 70 nm or more.
  • the average particle diameter of the silicon nanoparticles may be about 200 nm or less, about 150 nm or less, about 100 nm or less, about 50 nm or less, about 20 nm or less, or about 10 nm or less.
  • the average particle diameter of the silicon nanoparticles may be in a range of about 100 nm to about 150 nm.
  • Secondary particles of the composite of the silicon-based compound and the carbon-based compound may have an average diameter of about 5 um to about 18 um, for example, about 7 um to about 15 um, or for example, about 10 um to about 13 um.
  • a porous silicon composite cluster structure disclosed in Korean Patent Publication No. 10-2018-0031585 and a porous silicon composite cluster structure disclosed in Korean Patent Publication No. 10-2018-0056395 may be utilized.
  • Korean Patent Publication No. 10-2018-0031586 and Korean Patent Publication No. 10-2018-0056395 are incorporated herein by reference in their entireties.
  • a silicon-carbon-based compound composite may be a porous silicon composite cluster which includes a porous core including a porous silicon composite secondary particle and a shell including second graphene disposed on the core, wherein the porous silicon composite secondary particle may include an aggregate of two or more silicon composite primary particles, and the silicon composite primary particle may include silicon, silicon oxide (SiO x ) (wherein 0 ⁇ x ⁇ 2) disposed on the silicon, and first graphene disposed on the silicon oxide.
  • SiO x silicon oxide
  • a silicon-carbon-based compound composite may be a porous silicon composite cluster structure which includes a porous silicon composite cluster including a porous silicon composite secondary particle and a second carbon flake on at least one surface of the porous silicon composite secondary particle, and a carbon-based coating film including amorphous carbon disposed on the porous silicon composite cluster, wherein the porous silicon composite secondary particle may include an aggregate of two or more silicon composite primary particles, the silicon composite primary particle may include silicon, silicon oxide (SiO x ) (wherein O ⁇ x ⁇ 2) on at least one surface of the silicon, and a first carbon flake on at least one surface of the silicon oxide, and the silicon oxide may be present in a state of a film, a matrix, or a combination thereof.
  • the first carbon flake and the second carbon flake may each be present in a state of a film, a particle, a matrix, or a combination thereof.
  • the first carbon flake and the second carbon flake may each be graphene, graphite, a carbon fiber, graphene oxide, and/or the like.
  • the composite of the silicon-based compound and the carbon-based compound may be a composite having a structure in which silicon nanoparticles are arranged on a carbon-based compound, a composite having a structure in which silicon particles are included on a surface of a carbon-based compound and inside the carbon-based compound, or a composite in which silicon particles are coated with a carbon-based compound and included inside the carbon-based compound.
  • the carbon-based compound may be graphite, graphene, graphene oxide, or a combination thereof.
  • a shape of the lithium secondary battery is not particularly limited, and the lithium secondary battery may include a lithium ion battery, a lithium ion polymer battery, a lithium sulfur battery, and/or the like.
  • the lithium secondary battery may be manufactured through the following method.
  • a positive electrode is prepared.
  • a positive electrode active material composition in which a positive electrode active material, a conductive material, a binder, and a solvent are mixed is prepared.
  • the positive electrode active material composition may be applied directly on a metal current collector to prepare a positive electrode plate.
  • the positive electrode active material composition may be cast on a separate support, and then the film peeled off of the support may be laminated on a metal current collector to prepare the positive electrode plate.
  • the positive electrode is not limited to forms listed above and may have forms other than the above forms.
  • any material which is commonly utilized as a lithium-containing metal oxide in the art, may be utilized without limitation.
  • at least one composite oxide of lithium and a metal selected from among cobalt, manganese, nickel, and a combination thereof may be utilized.
  • a specific example of the positive electrode active material may include a compound represented by any one of Li a A 1-b B 1 b D 1 2 (wherein, 0.90 ⁇ a ⁇ 1.8, and 0 ⁇ b ⁇ 0.5); Li a E 1-b B 1 b O 2-c D 1 c (wherein, 0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, and 0 ⁇ c ⁇ 0.05); LiE 2-b B 1 b O 4-c D 1 c (wherein, 0 ⁇ b ⁇ 0.5, and 0 ⁇ c ⁇ 0.05); Li a Ni 1-b-c Co b B 1 c D 1 ⁇ (wherein, 0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05, and 0 ⁇ 2); Li a Ni 1-b-c Co b B 1 c O 2- ⁇ F 1 ⁇ (wherein, 0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05, and 0 ⁇ 2 ); Li a Ni 1-b-c Co b B 1 c O 2- ⁇ F 1 2
  • A may be Ni, Co, Mn, or a combination thereof
  • B 1 may be Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, a rare earth element, or a combination thereof
  • D 1 may be O, F, S, P, or a combination thereof
  • E may be Co, Mn, or a combination thereof
  • F 1 may be F, S, P, or a combination thereof
  • G may be Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, or a combination thereof
  • Q may be Ti, Mo, Mn, or a combination thereof
  • I may be Cr, V, Fe, Sc, Y, or a combination thereof
  • J may be V, Cr, Mn, Co, Ni, Cu, or a combination thereof.
  • a compound having a coating layer on a surface of the compound may be utilized, or a mixture of the compound and a compound having a coating layer may be utilized.
  • the coating layer may include a coating element compound of an oxide or hydroxide of a coating element, an oxyhydroxide of a coating element, an oxycarbonate of a coating element, or a hydroxycarbonate of a coating element.
  • a compound constituting the coating layer may be amorphous or crystalline.
  • the coating element included in the coating layer may include Mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr, or a mixture thereof.
  • any coating method may be utilized as long as the compound may be coated with such elements through a method (for example, a spray coating method or a dipping method) that does not adversely affect physical properties of the positive electrode active material. Because the coating method is well understood by those who work in the related field, a detailed description thereof will not be provided.
  • the conductive material may include carbon black, graphite fine particles, and/or the like, but embodiments of the present disclosure are not limited thereto. Any material utilized as a conductive material in the art may be utilized.
  • the binder may include at least one selected from vinylidene a fluoride/hexafluoropropylene copolymer, polyvinylidene fluoride (PVDF), polyacrylonitrile, polymethyl methacrylate, polytetrafluoroethylene, a mixture thereof, and a styrene butadiene rubber-based polymer, but embodiments of the present disclosure are not limited thereto. Any material utilized as a binder in the art may be utilized.
  • the solvent may include N-methyl pyrrolidone, acetone, and/or water, but embodiments of the present disclosure are not limited thereto. Any solvent utilized in the art may be utilized.
  • Contents (e.g., amounts) of the positive electrode active material, the conductive material, the binder, and the solvent are at levels that are commonly utilized in a lithium battery.
  • one or more selected from the conductive material, the binder, and the solvent may not be provided according to the utilization and configuration of a lithium battery.
  • a negative electrode active material composition is prepared by mixing a negative electrode active material, a conductive material, a binder, and a solvent.
  • the negative electrode active material composition may be applied directly on a metal current collector and dried to prepare a negative electrode plate.
  • the negative electrode active material composition may be cast on a separate support, and then a film peeled off of the support may be laminated on a metal current collector to prepare the negative electrode plate.
  • the negative electrode active material any material, which is utilized as a negative electrode active material for a lithium battery in the art, may be utilized.
  • the negative electrode active material may include at least one selected from a lithium metal, a metal capable of forming an alloy with lithium, a transition metal oxide, a non-transition metal oxide, and a carbon-based material.
  • the metal capable of forming an alloy with lithium may be silicon (Si), tin (Sn), aluminum (Al), germanium (Ge), lead (Pb), bismuth (Bi), antimony (Sb), a Si-Y alloy (wherein Y is an alkali metal, an alkaline earth metal, a Group 13 element, a Group 14 element, a transition metal, a rare earth element, or a combination thereof and is not Si), or a Sn-Y alloy (wherein Y is an alkali metal, an alkaline earth metal, a Group 13 element, a Group 14 element, a transition metal, a rare earth element, or a combination thereof and is not Sn).
  • the element Y may be magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), radium (Ra), scandium (Sc), yttrium (Y), titanium (Ti), zirconium (Zr), hafnium (Hf), rutherford
  • the transition metal oxide may be lithium titanium oxide, vanadium oxide, or lithium vanadium oxide.
  • the non-transition metal oxide may be SnO 2 , SiO x (wherein 0 ⁇ x ⁇ 2), and/or the like.
  • the carbon-based material may be crystalline carbon, amorphous carbon, or a mixture thereof.
  • the crystalline carbon may be graphite such as non-shaped (e.g., irregularly shaped), plate-shaped, flake-shaped, spherical, or fibrous natural graphite or artificial graphite.
  • the amorphous carbon may be soft carbon (low-temperature fired carbon) or hard carbon, mesophase pitch carbide, fired coke, and/or the like.
  • the conductive material and the binder in the negative electrode active material composition may be the same as those in the above-described positive electrode active material composition.
  • Contents (e.g., amounts) of the negative electrode active material, the conductive material, the binder, and the solvent are at levels that are utilized in a lithium battery.
  • one or more selected from the conductive material, the binder, and the solvent may not be provided according to the utilization and configuration of a lithium battery.
  • any separator utilized in a lithium battery may be utilized.
  • a separator having low resistance to the movement of ions in an electrolyte and an excellent or suitable electrolyte impregnation ability may be utilized.
  • the separator may include at least one selected from a glass fiber, polyester, Teflon, polyethylene, polypropylene, polytetrafluoroethylene (PTFE), and a combination thereof and may be in the form of a nonwoven fabric or a woven fabric.
  • a windable separator including polyethylene, polypropylene, and/or the like may be utilized in a lithium ion battery, and a separator having an excellent or suitable electrolyte impregnation ability may be utilized in a lithium ion polymer battery.
  • the separator may be prepared according to the following method.
  • a polymer resin, a filler, and a solvent are mixed to prepare a separator composition.
  • the separator composition may be applied directly on an electrode and dried to form the separator.
  • the separator composition may be cast on a support, and then a separator film peeled off of the support may be laminated on an electrode to form the separator.
  • the polymer resin utilized for preparing the separator is not particularly limited, and any material utilized in a binding material of an electrode plate may be utilized.
  • the polymer resin may include a vinylidene fluoride/hexafluoropropylene copolymer, PVDF, polyacrylonitrile, polymethyl methacrylate, or a mixture thereof.
  • a lithium battery 1 may include a positive electrode 3, a negative electrode 2, and a separator 4.
  • the positive electrode 3, the negative electrode 2, and the separator 4 may be wound or folded and accommodated in a battery case 5. Subsequently, an electrolyte may be injected into the battery case 5, and the battery case 5 may be sealed with a cap assembly 6 to complete the lithium battery 1.
  • the battery case 5 may have a cylindrical shape, a prismatic shape, a thin film shape, and/or the like.
  • the lithium battery 1 may be a large-sized thin film battery. In one or more embodiments, the lithium battery 1 may be a lithium ion battery.
  • the separator 4 may be disposed between the positive electrode 3 and the negative electrode 2 to form a battery structure.
  • the battery structure may be stacked in a bi-cell structure and then impregnated in an organic electrolyte, and an obtained battery structure may be accommodated in a pouch and sealed, thereby completing a lithium ion polymer battery.
  • a plurality of battery structures may be stacked to form a battery pack, and such a battery pack may be utilized in all devices requiring high capacity and high power.
  • the battery pack may be utilized in a laptop computer, a smartphone, an electric vehicle, and/or the like.
  • an increase in direct current internal resistance may be considerably reduced as compared with a lithium secondary battery adopting general nickel-rich lithium-nickel composite oxide as a positive electrode active material, thereby exhibiting excellent or suitable battery characteristics.
  • An operating voltage of a lithium secondary battery to which the positive electrode, the negative electrode, and the electrolyte are applied may have, for example, a lower limit of about 2.5 V to about 2.8 V and an upper limit of about 4.1 V or more, and the upper limit may be, for example, in a range of about 4.1 V to about 4.45 V.
  • the lithium secondary battery may be utilized in, for example, a power tool that moves by receiving power from an electric motor, an electric motor vehicle such as an electric vehicle (EV), a hybrid electric vehicle (HEV), or a plug-in hybrid electric vehicle (PHEV), an electric two-wheeled vehicle such as an electric bike (E-bike) or an electric scooter (E-scooter), an electric golf cart, a power storage system, and/or the like, but embodiments of the present disclosure are not limited thereto.
  • an electric motor vehicle such as an electric vehicle (EV), a hybrid electric vehicle (HEV), or a plug-in hybrid electric vehicle (PHEV)
  • E-bike electric bike
  • E-scooter electric scooter
  • an electric golf cart a power storage system, and/or the like, but embodiments of the present disclosure are not limited thereto.
  • alkyl group refers to a branched or unbranched aliphatic hydrocarbon group.
  • the alkyl group may be substituted or unsubstituted.
  • examples of the alkyl group may include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and/or the like, but embodiments of the present disclosure are not limited thereto.
  • each of the examples of the alkyl group may be optionally substituted.
  • the alkyl group may have 1 to 6 carbon atoms.
  • a C1-C6 alkyl group may include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a pentyl group, a 3-pentyl group, a hexyl group, and/or the like, but embodiments of the present disclosure are not limited thereto.
  • At least one hydrogen of alkyl may be substituted with a halogen, a C1-C20 alkyl group substituted with a halogen (for example, CCF 3 , CHCF 2 , CH 2 F, or CCl 3 ), a C1-C20 alkoxy group, a C2-C20 alkoxyalkyl group, a hydroxyl group, a nitro group, a CN group, an amino group, an amidino group, hydrazine, hydrazone, a carboxyl group or a salt thereof, a sulfonyl group, a sulfamoyl group, a sulfonic acid or a salt thereof, a phosphoric acid or a salt thereof, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C1-C20 heteroalkyl group, a C6-C20 aryl
  • alkenyl group may refer to a C2 to C20 hydrocarbon group having at least one carbon-carbon double bond.
  • alkenyl group may include an ethenyl group, a 1-propenyl group, a 2-propenyl group, a 2-methyl-1-propenyl group, a 1-butenyl group, a 2-butenyl group, a cyclopropenyl group, cyclopentenyl, cyclohexenyl, cycloheptenyl, and/or the like, but embodiments of the present disclosure are not limited thereto.
  • the alkenyl group may be substituted or unsubstituted.
  • the alkenyl group may have 2 to 40 carbon atoms.
  • alkynyl group may refer to a C 2 to C 20 hydrocarbon group having at least one carbon-carbon triple bond.
  • examples of the alkynyl group may include an ethynyl group, a 1-propynyl group, a 1-butynyl group, a 2-butynyl group, and/or the like, but embodiments of the present disclosure are not limited thereto.
  • the alkynyl group may be substituted or unsubstituted.
  • the alkynyl group may have 2 to 40 carbon atoms.
  • a substituted group is derived from an unsubstituted parent group in which at least one hydrogen atom is substituted with another atom or a functional group.
  • a functional group is deemed to be "substituted,” it is meant that the functional group is substituted with at least one substituent independently selected from a C1-C20 group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C1-C20 alkoxy group, a halogen, a CN group, a hydroxyl group, and a nitro group.
  • the functional group may be substituted with at least one selected from the above-described substituents.
  • halogen may include fluorine, bromine, chlorine, iodine, and/or the like.
  • alkoxy may refer to "alkyl-O-", and alkyl may be defined above.
  • alkoxy group may include a methoxy group, an ethoxy group, a 2-propoxy group, a butoxy group, a t-butoxy group, a pentyloxy group, a hexyloxy group, and/or the like.
  • At least one hydrogen of the alkoxy may be substituted with the same substituent as the above-described alkyl group.
  • heteroaryl may refer to a monocyclic or bicyclic organic group including at least one heteroatom selected from N, O, P, and S, wherein the remaining ring atoms are all carbon.
  • a heteroaryl group may include, for example, one to five heteroatoms, and in some embodiments, may include a five- to ten-membered ring.
  • S or N may be oxidized to have one or more suitable oxidation states.
  • Non-limiting examples of the heteroaryl may include thienyl, furyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, isooxazol-3-yl, isooxazol-4-yl, isooxazol-5-yl, 1,2,4-triazol-3-yl, 1,2,4-triazol-5-yl, 1,2,
  • heteroaryl may include an embodiment in which a heteroaromatic ring is selectively fused to at least one of an aryl group, a cycloaliphatic group, or a heterocyclic group.
  • carbon ring may refer to a saturated or partially unsaturated non-aromatic monocyclic, bicyclic, or tricyclic hydrocarbon group.
  • Non-limiting examples of monocyclic hydrocarbon may include cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, and/or the like.
  • bicyclic hydrocarbon may include bornyl, decahydronaphthyl, bicyclo[2.1.1]hexyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.1]heptenyl, and/or bicyclo[2.2.2]octyl.
  • Non-limiting examples of tricyclic hydrocarbon may include adamantly and/or the like.
  • At least one hydrogen in the carbon ring may be substituted with a substituent similar to the above-described alkyl group.
  • LiPF 6 1.15 M LiPF 6 was added to a mixed solvent of EC, EMC, and DMC having a volume ratio of 20:40:40 to prepare an electrolyte.
  • An electrolyte was prepared in substantially the same manner as in Comparative Example 2, except that, with respect to 100 wt% of the total weight of the electrolyte of Comparative Example 2, 3 wt% of Compound A as an additive was further added to the electrolyte.
  • Electrolytes were prepared in substantially the same manner as in Example 3, except that Compound B, Compound C, Compound D, Compound E, and Compound F were utilized as additives instead of Compound A, respectively.
  • Electrolytes were each prepared in substantially the same manner as in Example 4, except that contents of Compound B were respectively changed into 5 wt% and 7 wt% with respect to 100 wt% of the total weight of the electrolyte.
  • An electrolyte was prepared in substantially the same manner as in Comparative Example 2, except that Compound J was utilized as an additive in the electrolyte of Comparative Example 2, and a content (e.g., amount) of the additive was 3 wt% with respect to 100 wt% of the total weight of the electrolyte.
  • An electrolyte was prepared in substantially the same manner as in Comparative Example 2, except that Compound K was utilized as an additive in the electrolyte of Comparative Example 2, and a content (e.g., amount) of the additive was 3 wt% with respect to 100 wt% of the total weight of the electrolyte.
  • 98 wt% of graphite particles, 1 wt% of carboxymethyl cellulose (CMC), and 1 wt% of a styrene-butadiene rubber (SBR) aqueous dispersion binder were mixed, put into distilled water, and then stirred for 60 minutes utilizing a mechanical stirrer to prepare slurry of a negative (electrode) active material.
  • the slurry was applied to a thickness of about 60 um on a copper current collector with a thickness of 10 um utilizing a doctor blade, dried in a hot air dryer at a temperature of 100°C for 0.5 hours, dried once more for 4 hours under conditions of vacuum and a temperature of 120°C, and roll-pressed to prepare a negative electrode.
  • a mixture density (E/D) of the negative electrode was 1.55 g/cc, and a loading level (L/L) thereof was 14.36 mg/cm 2 .
  • a positive electrode was prepared according to the following procedure.
  • the slurry was applied to a thickness of about 60 um on an aluminum current collector with a thickness of 20 um utilizing a doctor blade, dried in a hot air dryer at a temperature of 100 °C for 0.5 hours, dried once more for 4 hours under conditions of vacuum and a temperature of 120°C, and roll-pressed to prepare the positive electrode.
  • a mixture density (E/D) of the positive electrode was 3.15 g/cc, and a loading level (L/L) thereof was 27.05 mg/cm 2 .
  • a lithium secondary battery (pouch cell having about 40 mAh) was manufactured utilizing a polyethylene separator (thickness of 16 um) as a separator and utilizing the electrolyte of Example 3 as an electrolyte.
  • Lithium secondary batteries (pouch cells) were each manufactured in substantially the same manner as in Manufacturing Example 1, except that the electrolytes prepared in Examples 4 to 9 were respectively utilized instead of the electrolyte prepared in Example 3.
  • a lithium secondary battery (pouch cell) was manufactured in substantially the same manner as in Manufacturing Example 1, except that the electrolyte prepared in Example 10 was utilized instead of the electrolyte prepared in Example 3.
  • Lithium secondary batteries (pouch cells) were each manufactured in substantially the same manner as in Manufacturing Example 1, except that the electrolytes prepared in Comparative Examples 2 to 4 were respectively utilized instead of the electrolyte prepared in Example 3.
  • a three-electrode beaker cell was constructed utilizing each of the electrolytes of Examples 1 and 2 and Comparative Example 1, and then a linear sweep voltammetry test was performed to evaluate an oxidation behavior of the electrolyte at a working electrode. Results thereof are shown in FIG. 2.
  • a glassy carbon electrode was utilized as the working electrode, and a lithium metal was utilized as each of a counter electrode and a reference electrode to assemble the three-electrode beaker cell, and the three-electrode beaker cell was left for 1 hour to then perform measurement.
  • a voltage was applied at a rate of 1 mV/sec up to an open circuit voltage (OCV) of 6 V (vs. Li/Li + ) to perform scanning.
  • OCV open circuit voltage
  • Example 1 and the electrolyte of Example 2 were oxidized near about 5.2 V and 5.4 V, respectively.
  • an additive may be decomposed in an overcharge environment (high voltage) to suppress or reduce a voltage rise of a battery and contribute to an improvement in the safety of a cell.
  • the lithium secondary batteries manufactured according to Manufacturing Examples 1 to 7 and Comparative Manufacturing Examples 1 to 3 were each subjected to a formation operation, and an overcharge test was prepared for the lithium secondary batteries subjected to the formation operation in a discharged state.
  • the overcharge test was performed utilizing Biologics, and an amount of gas after overcharging was measured utilizing the Archimedes’principle.
  • Overcharge protocol after discharging at 0.2C and 2.5 V, overcharging was performed under c/o conditions of 1C, 6 V, and 5 hours. After the overcharging was performed, a cell was left for about three hours to then perform a formation operation according to the Archimedes’principle, and then an amount of gas caused by the overcharging after the overcharging was confirmed through a difference in volume of the amount of gas. Results thereof are shown in Table 1.
  • the lithium secondary batteries manufactured according to manufacturing Examples 1 to 8 and Comparative manufacturing Examples 1 to 3 were each subjected to a formation operation at a temperature of 45 °C, the lithium secondary batteries subjected to the formation operation were charged at a constant current rate of 1.5 C until a voltage reached 4.2 V (vs. Li), and then, in a constant voltage mode, while 4.2 V was maintained, the charging was cut off at a current rate of 0.05 C. Subsequently, the lithium secondary batteries were discharged at a constant current rate of 0.5 C until the voltage reached 2.5V (vs. Li) during discharging. Such a charging/discharging cycle was repeated 300 times. The lithium batteries were rested for 10 minutes after each charging/discharging cycle. Results thereof are shown in Table 2.
  • a capacity retention rate at a 300 th cycle is defined by Equation 1.
  • size or “particle diameter” indicates a diameter or an diameter
  • size or “particle diameter” indicates a major axis length or an average major axis length
  • the diameter (or size) of the particles may be measured utilizing a scanning electron microscope or a particle size analyzer.
  • the particle size analyzer for example, HORIBA, LA-950 laser particle size analyzer, may be utilized.
  • the average particle diameter (or size) is referred to as D50.
  • D50 refers to the average diameter (or size) of particles whose cumulative volume corresponds to 50 vol% in the particle size distribution (e.g., cumulative distribution), and refers to the value of the particle size corresponding to 50% from the smallest particle when the total number of particles is 100% in the distribution curve accumulated in the order of the smallest particle size to the largest particle size.
  • the terms “substantially”, “about”, or similar terms are used as terms of approximation and not as terms of degree, and are intended to account for the inherent deviations in measured or calculated values that would be recognized by those of ordinary skill in the art. “About”as used herein, is inclusive of the stated value and means within an acceptable range of deviation for the particular value as determined by one of ordinary skill in the art, considering the measurement in question and the error associated with measurement of the particular quantity (i.e., the limitations of the measurement system). For example, "about” may mean within one or more standard deviations, or within ⁇ 30%, 20%, 10%, 5% of the stated value.
  • any numerical range recited herein is intended to include all sub-ranges of the same numerical precision subsumed within the recited range.
  • a range of "1.0 to 10.0" is intended to include all subranges between (and including) the recited minimum value of 1.0 and the recited maximum value of 10.0, that is, having a minimum value equal to or greater than 1.0 and a maximum value equal to or less than 10.0, such as, for example, 2.4 to 7.6.
  • Any maximum numerical limitation recited herein is intended to include all lower numerical limitations subsumed therein and any minimum numerical limitation recited in this specification is intended to include all higher numerical limitations subsumed therein. Accordingly, Applicant reserves the right to amend this specification, including the claims, to expressly recite any sub-range subsumed within the ranges expressly recited herein.

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Abstract

L'invention concerne un électrolyte pour une batterie secondaire au lithium et une batterie secondaire au lithium comprenant l'électrolyte. L'électrolyte pour une batterie secondaire au lithium peut comprendre un sel de lithium, un solvant organique et un additif représenté par la formule 1, où au moins un élément choisi parmi R1 à R6 peut être un groupe alkyle en C1-C5 comprenant un groupe cyano, et un ou deux éléments choisis parmi R1 à R6 peuvent chacun être un groupe alkyle en C1-C5 fluoré. (Formule 1)
PCT/KR2023/018273 2022-11-14 2023-11-14 Électrolyte pour batterie secondaire au lithium et batterie secondaire au lithium le comprenant WO2024106910A1 (fr)

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Citations (4)

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KR100810634B1 (ko) * 2006-11-30 2008-03-06 삼성에스디아이 주식회사 리튬 이차 전지용 전해액 및 이를 포함하는 리튬 이차 전지
KR20110136085A (ko) * 2010-06-14 2011-12-21 주식회사 엘지화학 리튬 이차전지
CN111525191A (zh) * 2020-04-29 2020-08-11 宁德新能源科技有限公司 一种电解液及电化学装置
WO2022056731A1 (fr) * 2020-09-16 2022-03-24 宁德新能源科技有限公司 Électrolyte et dispositif électrochimique le contenant

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KR20110136085A (ko) * 2010-06-14 2011-12-21 주식회사 엘지화학 리튬 이차전지
CN111525191A (zh) * 2020-04-29 2020-08-11 宁德新能源科技有限公司 一种电解液及电化学装置
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